S-(amidocarbonyl)-methyl-O-alkyl-monothiophosphoric acid ester amides

ABSTRACT

S-(amidocarbonyl)-methyl-O-alkyl-monothiophosphoric acid ester amides of the formula   in which R and R&#39;&#39; each independently is alkyl of 1 to 6 carbon atoms, R&#39;&#39;&#39;&#39; is alkyl or alkenyl of 1 to 6 carbon atoms optionally carrying at least one chlorine, C1-C6 alkoxy, C1-C6 alkylmercapto or nitrile radical, R&#39;&#39;&#39;&#39;&#39;&#39; is hydrogen or acyl, with the proviso that R&#39;&#39;&#39;&#39;&#39;&#39; is not hydrogen if R&#39;&#39;&#39;&#39; is unsubstituted alkyl, or R&#39;&#39;&#39;&#39; and R&#39;&#39;&#39;&#39;&#39;&#39; conjointly with the nitrogen atom to which they are attached form a heterocyclic ring, WHICH POSSESS INSECTICIDAL AND ACARICIDAL PROPERTIES.

United States Patent Stiilzer et al.

[ Sept. 23, 1975 S-(AMIDOCARBONYL )-METHYL-O- ALKYL-MONOTHIOPHOSPHORICACID ESTER AMIDES Inventors: Claus St'dlzer, Wuppertal,

Vohwinkel; Ingeborg Hammann, Cologne; Giinter Unterstenhiifer, Opladen,all of Germany Primary ExaminerAnton H. Sutto Attorney, Agent, orFirm-Burgess, Dinklage & Sprung [57] ABSTRACT S-(amidocarbonyl)-methyl-O-alkyl-monothiophosphoric acid ester amides ofthe formula in which R and R each independently is alkyl of 1 to 6carbon atoms,

R" is alkyl or alkenyl of 1 to 6 carbon atoms optionally carrying atleast one chlorine, C -C alkoxy, C C alkylmercapto or nitrile radical,

R is hydrogen or acyl, with the proviso that R' is not hydrogen if R" isunsubstituted alkyl, or

R" and R conjointly with the nitrogen atom to which they are attachedform a heterocyclic ring,

which possess insecticidal and acaricidal properties.

5 Claims, No Drawings S-(AMIDOCARBONYL)-METHYL--ALKYL-MONOTHIOPHOSPHORIC ACID ESTER'AMIDES The present invention relates toand has for its-ob-v jects the provision of particular new S-(amidocarbonyl)-methyl-O-alkyl-monothiophosphoric acid ester amides,which possess insecticidal or acaricidal properties, active compositionsin the form of mixtures of such compounds with solid and liquiddispersible carrier vehicles, and methods for producing such compoundsand for using such compounds in a new way especially for combatingpests, e.g., insects and acarids, with other and further objectsbecoming apparent from a study of the within specification andaccompanying examples.

It is known from German Published Specification DAS 3,019,250 that thereaction products of O-alkyl-N- monoalkylamido-monothiophosphoric acidsalts with substituted halogenomethyl compounds are distinguished by aninsecticidal and acaricidal action.

The present invention provides, as new compounds, theS-(amidocarbonyl)-methylanonothiophosphoric acid ester amides of thegeneral formula P R" (l) R'NH/ \S-CH,(I-N R in which R and R eachindependently is alkyl of l to 6 carbon atoms,

R" is alkyl or alkenyl of l to 6 carbon atoms optionally carrying atleast one chlorine, C C, alkoxy, C C, alkylmercapto or nitrile radical,R' is hydrogen or acyl with the proviso that R"' is not hydrogen if R"is unsubstituted alkyl, or

R" and R conjointly with the nitrogen atom to which they are attachedform a heterocyclic ring.

Surprisingly, the S-(amidocarbonyl)-methylmonothiophosphoric acid esteramides of the formula (I) possess a substantially better insecticidaland acaricidal action than the known S-(amidocarbonyl)-methyl-monothioand -dithiophosphoric acid 0,0- dialkyl esters, which inrespect of both structure and type of activity are the nearestcomparable compounds and also the best-known commercially availableproducts of this class of substance. The compounds according to theinvention thus represent an enrichment of the art.

Preferably, R and R are each straight-chain or branched lower alkyl withl to 4 carbon atoms (namely methyl, ethyl, isoor n-propyl or n-, iso-,sec.- or ten.- butyl); R" is lower alkyl with l to 4 carbon atoms whichmay be carrying one or more substituents selected from chlorine, C -Calkoxy, C -C alkylmer capto and nitrile, or is allyl; R' is hydrogen oran acyl radical such as formyl, lower 'alkanoyl, benzoyl, carboloweralkoxy or carbophenoxy, especially formyl, acetyl, propionyl, butyryl,isobutyryl or benzoyl; and R" and R, when forming a heterocyclic ring,are piperidino, morpholino, thiazolino or diazolino.

The present invention also provides a process for the production of anS-(amidocarbonyl)-methyl-monothiophosphoric acid ester amide of theformula (I) in which an acid salt of the general formulaO-alkyl-N-monoalkylamido-monothiophosphoric 1,135,905 and U.S. PatentSpecification' is reacted with a halogenoacetic acid amide of thegeneral formula in which formulas R, R, R" and R' have theabove-mentioned meanings, Hal is halogen, preferably bromine orchlorine, and M is an alkali metal equivalent, alkaline earth metalequivalent or optionally alkylsubstituted ammonium equivalent.

If the sodium salt of O-ethyl-N-monoisopropylamidomonothiophosphoricacid and chloroacetic acid morpholide are used as starting materials,the course of the reaction can be represented by the following equation:

The following may be mentioned as examples of O-alkyl-N-monoalkylamidomonothiophosphoric acid salts of the formula (ll):the alkali metal salts, alkaline earth metal salts and optionallyalkyl-substituted ammonium salts of O-methyl-N-methyl, O-methyl-N-propyl-, O-methyl-N-isopropyl-, O-ethyl-N-methyl-, O- ethyl-N-ethyl-,O-ethyl-N-isopropyland O-butyl-N- ethylamide-monothiophosphoric acids.

These salts and the halogenoacetic acid derivatives (Ill) are known andcan be produced according to customary methods.

The preparative process for the new compounds (I) is preferably carriedout with the conjoint use of a suitable solvent or diluent. Practicallyall inert organic solvents can be used for this purpose, especiallyaliphatic and aromatic, optionally chlorinated hydrocarbons, such asbenzene, toluene, xylenes, benzine, methylene chloride, chloroform,carbon tetrachloride and chlorobenzene; ethers, for example diethylether, dibutyl ether and dioxane; ketones, for example acetone, methylethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone,nitriles, such as acetonitrile and propionitrile; and alcohols, forexample methanol, ethanol and isopropanol. Water is also suitable as thesolvent in certain cases.

The reaction temperature can be varied within a fairly wide range. Ingeneral the reaction is carried out at from-0 to C, preferably at from15 to 60C.

To carry out the process, the starting materials are in most casesemployed in equimolar amounts. An excess of one or other reactioncomponent results in no substantial advantages. The reaction ispreferably carried out in the presence of one of the above-mentionedsolvents, at. the indicated temperatures, and. the reaction mixture isworked up in the usual manner after stirring for several hours.

The substances according to the invention are in most cases obtained inthe form of colorless to slightly colored viscous water-soluble oils orcrystals which, in general, cannot be distilled without decompositionbut can be freed of the last volatile constituents by socalled slightdistillation, that is to say prolonged heating under reduced pressure tomoderately elevated temperatures, and can be purified in this way. Theyare characterized, above all, by the refractive index and, in the caseof the solid compounds, by the melting point.

As has already been mentioned, the new S-(amidocarbonyl)-methyl-monothiophosphoric 1 acid ester amides aredistinguished by an outstanding insecticidal and acaricidal activityagainst plant pests and pests harmful to health. They possess a goodaction against both sucking and biting insects and against mites(Acarina). At the same time they display only a slight phytotoxicity.For these reasons the compounds according to the invention may besuccessfully employed as pesticides in plant protection and in thehygiene field.

To the sucking insects there belong, in the main,- aphids (Aphidae) suchas the green peach aphid (Myzus persicae), the bean aphid (Doralisfabae), the bird cherry aphid (Rhopalosiphum padi), the pea aphid(Macrosiphum pisi) and the potato aphid (Macrosiphum solanifolii), thecurrant gall aphid (Cryptomyzus korschelti), the rosy apple aphid(Sappaphis mali), the mealy plum aphid (Hyalopterus arundinis) and thecherry black-fly (Myzus cerasi); in addition, scales and mealybugs(Cocci a), for example the oleander scale v(Aspidirnus hederae)'and thesoft scale (Lecanium hes- 1 peridum) as well as the grape mealybug(Pseudococcus ,In the case ofthe biting insects, above ,all there shouldbe mentioned butterfly caterpillars (Lepidoptera) such as thediamond-back moth (Plu tella m aculipennis), the gypsy moth (Lymar xtria dis-par), the browntail moth (Euproctis ch'rysorrhaeaj and tentcaterpillar (Malacosoma neustria); further, the cabbage moth (Mamestrabrassicae) and-the cutworm (Agrotis segetum), the large white butterfly(Pieris brassicae), the small winter moth (Cheimatobia brumata), thegreen oak tortrix moth (Tortrix viridana), thefall armyworm (Laphygmafrugiperda) and cotton worm (Pro denia lirura), the ermine moth(Hyponomeuta padellh), the Mediterranean flour moth (Ephestiak'uhniella) and greater wax moth (Galleria mellonella).

Also to be classed with the biting'insects are'beetles (Coleoptera),forexample the granary lweevil, .(Sitobeetle (LeptinbtarsadecemlineataX-the dock beetle (Gastrophysa viridula), the mustard beetle(Phaedon .noptera' such as ants, for example philus granarius Calandragranaria); the Colorado coch lea riad the, blossom beetle Meligerhesaeneus), the r as berry beetle (Byturus tomenrosus), the bean weevilBruchidiur Aca thoscelides obtectus), V the leather :beetle (Dermestesfrischi), the khapra beetle Trog oglerm granarium the flour beetle(Tribqlium castaneu m), the northern corn billbug (Calandra orSitophilus zedmais), the drugstore beetle (Stegobium paniceum), the.yellow mealworm (Tenebrio ,r nolitor) and the- .sawtoothed grain beetle(Oryzaephilussurinamensis), and also species.- liying in the soil, forexample wireworms (Agriotesspea) and, larvae of the cockchafer(Melolantha'melplontha cockroaches, such as the German cockroach(Blattella germanica), American cockroach (Periplaneta americana),Madeira cockroach (Leucophaea or Rhyparobiir mqderae), orientalcockroach (Bla ttq orientalis), the] giant cockroach (Blaberusgigqnreusfand the black giant cockroach (Blaberus fixscus) ,as well asHenschoutedenia flexivitta; further Orthoptera, for example the housecricket (Achetadomest icus); termites such as the easternsubterraneantermite.Reticulitermes flavipes) and Hymethe garden ant(Lasius niger).- v

The Diptera comprise essentially the flies, such as the vinegar fly(Drosophila melanogaster), the Mediterranean fruit fly (Ceratitiscapitata the house fly (Musca domestica), the little house fly (Fanniacanicularis), the black blow fly (Phormia regina) and bluebottle fly(Calliphora erythrocephala) as well as the stable fly (Stomoxyscalcitrans); further, gnats, for example mosquitoes such as the yellowfever mosquito (Aedes aegypti),

'the northern'hou'se mosquito (Ciilex pipiens) and the malaria mosquito(Anopheles stephensi).

With the mites (Acari) there are classed, in particular, the spidermites (Tetranychidae) such 'as the twospotted spid'er rnite (Tetran'ychus urticae) and the European red mite (Para tetranychus pilosusPanonychus ulmi), gall mi tes, for example the blackcurrant gall i mite(Eriopliyesribis) and tarsoneinids, for example the ,broad mite(flej'mita'rsonemus latus) and the cyclamen mite (Tarsqnemizsp'allidus); finally, ticks', suchas the -relapsing fever tick(Ofnithqdorus r'ri oubata).

When applied against pests harmful to health and pests of storedproducts, particularly flies and mosquitoes, the'active compounds arealso distinguished by an outstanding residual activity on wood'and clay,as well asa good stability to alkali on 'lirned substrates.

;The active compounds according to the instant invention can. beutilized, if desired,in the form of the usual formulations orcompositions with conventional inert (i.e plant compatible orherbicidally inert) pesticide diluents or extenders, i.e.', diluen'ts,carriers or extenders of the type usable in conventional pesticideformulations or compositions, e.g., conventional pesticide dispersiblecarrier vehicles such as gases, solutions, emulsions, suspensions,emulsifiable concentrates, spray powders, pastes, soluble powders,dusting agents, granules, etc. These are prepared in known manner, forinstance by extending the active compounds with conventional'ipesticidedispersible liquid diluent carriers and/or'dispe'rs'ible solid carriersoptionally with the use of carrier vehicle assistants, e.g.,conventional pesticide surface-active agents, 7 includingemulsifying agents and/or dispersing agents, whereby, for example, inthe case whe re water is used as diluent, organic solvents may be addedas auxiliary solvents. The following may be chiefly considered for useas'conventional carrier vehicles for this purpose; aerosol propellantswhidl'i are gaseous at normal temperature's and pressures, sueh'a's'etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g.,chlorobenzenes, etc.), cycloalkanes (e.g., cyclohexane, etc.), paraffins(e.g. petroleum or mineral oil fractions), chlorinated aliphatichydrocar bons (e.g., methylene chloride, chloroethylenes, etc.),alcohols (e.g., methanol, ethanol, propanol, butanol, glycol, etc.) aswell as ethers and esters thereof (e.g., glycol monomethyl ether,etc.),.amines (e.g., ethanolamine, etc.), amides (e.g. dimethylformamide, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.),acetonitrile, ketones (e.g., acetone, methyl ethyl ketone, methylisobutyl ketone, cyclohexanone, etc.), and/or water; as well as inertdispersible finely divided solid carriers, such as ground naturalminerals (e.g., kaolins, clays, alimina, silica, chalk, i.e. calciumcarbonate, talc, attapulgite, montmorillonite, 'kieselguhr, etc.) andground synthetic minerals (e.g. highly dispersed silicic acid,silicates, e.g. alkali silicates, etc.); whereas the following may bechiefly considered for use as conventional carrier vehicle assistants,e.g. surface-active agents, for this purpose: emulsifying agents, suchas non-ionic and- /r anionic emulsifying agents (e.g. polyethylene oxideesters of fatty acids, polyethylene oxide ethers of fatty alcohols,alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolyzates,etc., and especially alkyl arylpolyglycol ethers, magnesium stearate,sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfitewaste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other insecticides andacaricides or rodenticides, fungicides, bactericides, nematocides,herbicides, fertilizers, growth-regulating agents, etc., if desired, orin the form of particular dosage preparations for'specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which arethus ready for use.

As concerns commercially marketed preparations, these generallycontemplate'carrier composition mixtures in which the active compound ispresent in an .amount substantially between about 01-95% by weight, andpreferably 05-90% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field' applicationgenerally, contemplate those in which the active compound is present inan amount substantially between about 0.000l-l0%, preferably 0.01-l%, byweight of the mixture. Thus, the present invention contemplates over-allcompositions which comprises mixtures of a conventional dispersiblecarrier vehicle such as (l) a dispersible inert finely divided carriersolid, and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/or water preferably including a surface-active effectiveamount of a carrier vehicle assistant, e. g. a surface-active agent,

such as an emulsifying agent and/ora dispersing agent,

and an amount of the active compound which is effec- The activecompounds can also be 'used in accordancewith -the"well known.ultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing 1 equipment, in finelydivided form, e. g., average particle diameter of from 50-100 microns,or even less, i.e., mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 15 to lOOO g/hectare, preferably 40to 600'g/hectare, are sufficient. In this process it is possible to usehighly eoncentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activecompound or even the 100% active substance alone, e.g. about 20100% byweight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling,combating or controlling pests, e.g., insects and acarids, whichcomprises applying to at least one of correspondingly (a) such insects,(b) such acarids, and (c) the corresponding habitat thereof, i.e. thelocus to be protected, a correspondingly combative or toxic amount, i.e.an insecticidally or acaricidally effective amount, of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring,

r fumigating, dressing, encrusting, and the like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of theparticular new compounds of the present invention are illustrated,without limitation, by the following examples:

EXAMPLE 1 Phaedon test (systemic long-term action) Solvent: 3 parts byweight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycolether 7 u I i To produce an appropriate preparation of active compound,.1 part by weight of active compound was mixed with the indicated amountof solvent which contained the indicated amount of emulsifier and theconcentrate was diluted. with water to the desired concentration of.025% of active .compound. I

Cabbage plants (Brassica ioleracea) were watered with 50 ml portions ofthe active-compound preparation in such a way that the active-compoundpreparation entered the soil without wetting the leaves of the cabbageplants. The active compound was taken up by the cabbage plants from thesoiland thus reached the leaves. 12.5 mg of active compound were usedpergof soil (weighed air-dry).

After the indicated times, the plants were infested "with mustard beetlelarvae '(Phaedon cochleariae) and their destruction was in each casedetermined after 3 days as a percentage. [00% means that all of thelarve were killed and 0% means that none of the larvae were killed.

The active compounds, active-compound concentra- Cabbage plants(Brassica oleracea) were watered tions, evaluation times and results canbe seen from the with 50 ml portions of the active-compoundpreparafollowing Table 1: tion in such a way that the active-compoundprepara- Table l Longtcrm action after watering. P/lUL'lIOIl('(IC/ll'lll'ilfl Blzlssicu olemu'u) Active compound mg of '7!destruction after days:

active compound per I g of soil (weighed air'Llry) l0 I7 24 27 31 34 4]48 o CH.,o W 12.5 100 so /PS-CH. .-C-NHCH, CH,,O (known) (A) c.,H .,o 0

12.5 100 100 mo 70 so 50 CH,,NH/ S-CH:fi-NHCCH cur-,0 o

\P/ 125 I00 100 m0 100 l()() 100 100 I00 100 i-C:|H:-NH s-CH. C

12.5 100 100 m0 100 um mo 20 C. .H ,O P O iC;,.H -NH\S-CH:CNHCH2CH2-OCH=,

C:H,-,O\P/O CH 125 m0 100 so 70 50 60 iC;,H NH s cH,-|cl NH c cH,

12.5 100 I00 100 100 90 so 40 i-C -,H NH \SCH. CN\

H CH0 0 EXAMPLE 2 tion entered the soil without wetting the leaves ofthe cabbage plants. The active compound was taken up by the cabbageplants from the soil and thus reached the Myzus test (systemic long-termaction) leaves. 12.5 mg of active compound were used per 100 Solvent: 3parts by weight of acetone g of soil (weighed air-dry). Emulsifierz 1parts by weight of alkylaryl polyglycol After the indicated times, theplants were infested ether with aphids (Myzus persicae) and theirdestruction was TO produce an appropriate prepar i n O active in eachcase determined after 3 days as a percentage. mp 1 p y igh f activecompound was 100% means that all the aphids were killed and 0% mixedwith the indicated amount of solvent which conmeans that none of theaphids were killed. tained the indicated amount of emulsifier and thecon- The active compounds, active-compound concentracentrate was dilutedwith water to the desired concentions, evaluation times and results canbe seen from the tration of 0.025% of active compound. following Table2:

Table 2 (Long-term action after watering: Myzus persivae Bruxxicuoleraccu) Active compound mg of "/1 destruction after days:

active compound per I00 g of soil (weighed air-dry) I7 20 24 3! 38 4] 4548 52 O cH..0 ll

PSCH:CNHCH 12.5 100 i 0 (H O (known) (A) (Long-term action afterwatering: Myzus perxicuu Bruxxicu uluruwu) Active compound mg of 71destruction after days:

active compound per I00 g of soil (weighed air-dry) 17 20 24 3s 41 45 4x52 s 0 Q11 0 u ll 6 S-CH2CNHCH,, 12.5 1011 1011 100 100 75 H1 (known)(B) C2H,,O 0

P 12.5 100 1110 100 100 1110 100 100 50 50. CH,,-NH SCH2C-NH-CH2OCH,,

C2H .,O o

\P 12.5 100 1110 100 1011 1011 100 1110 100 100 CH,,--NHSCH2C-NH-CH2-CH20CH,,

C. .H -,O 0 C 1,

P CH:,NH/ S-CH -iNHCCH 12.5 11111 1011 1011 11111 100 11111 1110 10111110 c. .n,,o o g P c11=, CH;,NH/ s C1-11 -N 12.5 11111 1011 11111 111111110 11111 1011 11111 1011 c l-i o q 4 CH,,NH/ \SCH2--(I"-NC-OC2H,, 12.51110 1110 1011' 1110 1110 1011 100 1110 11111 C. H -,o ,0 I I g v i C,H,-NH fSCH- ([i-NH'CH. OCH=, 12.5 100 1'110 100' 1011 100 .100 100 1011100 P 12.5 100 1011 100 100 1110 11111 0 iC,,H,NH \S-CH2CNH'CC'H,-, ll

c. H -,o "o i -C H -NH/ s cH. c -N- 12.5 11111 1011 1011 1110 100 1110100 100 100 c H ,0 ,0 1 \S-CH2 N/ 12.5 1110 11111 11111 1110 100 111111110 1110 11111 EXAMPLE 3 Hop plants (Humulus Iupulus), which wereheavily infested with the hop-damson aphid (Phorodon humu- Phorodon test(contact action resistant) Solvent: 3 parts by weight of acetoneEmulsifier: 1 part by weight of alkylaryl polyglycol ether To produce asuitable preparation of active compound, 1 part by weight of the activecompound was mixed with the stated amount of solvent containing the II/resistant), were sprayed with the preparation of the active compounduntil dripping wet.

After the specified periods of time, the degree of destruction wasdetermined as a percentage. means that all the aphids were killedwhereas 0% means that none of the aphids were killed.

The active compounds, the concentrations of the accompounds, theevaluation times and the results can be seen from the following Table 3:Cabbage plants (Brassica oleracea), which had been Table 3 (llmruzlmilmmu/i/ resistant) Active compound Active Degree of compound 1concentration destruction in /i in A after 1 day 0- cH .,0 a ll S-CH.,1-11-1 c1-1 0.1 50 01 0 0.02 (known) (A) c n o 0 cH'j P x 0.1 100CHF-NH/ \S- CH2CNHCCH;, 0.02 100 0.004 100 (N (12) P CH,,NH/ SCH C-N o0.1 100 0.02 98 0 (7) C2H -,O 0

0.1 100 iC:,H i--C;;H NH S CH. N\ 0.02 100 CCH,, 0.004 60 o EXAMPLE 4heavily infested with peach aphids (Myzus persicae/re- Myzu's test(Contact action) resistant sistant), were sprayed with the preparationof the ac- Solvent: 3 parts by weight of acetone five ompound untildripping-wet. I Emulsifier: 1 part by weight of alkylaryl poly'gly lAfter the specified penods of time, the degree of de- 1 struetion wasdetermined as a percentage: 100% means ether To produce a suitable(preparation of active comthat the P w lil l y. q sflb "@3 ihal pound, 1part by weight of the" active compound was "9"? f 1.6 ph d W9? li mixedwith the stated amount of-solventtcontaining the The active compounds,the concentrations of the acstated amount of emulsifier and theconcentrate was 40 tive compounds, the evaluation times and the resultsdiluted with water to the desired concentration, I .b Seen f h f ll wingTable 4:

'-.Table1 4. w

(Mp-1m pt 'rsic'm' resistant) Active compound Active Degree of compoundy 1 concentration destruction in in A /1 after I day 0 c1-| .,o II 0.1P-SCH. ,C-NH-CH,, 0.02 20 Cu e (known) (A) PSCH2CNHCH,, 0.1 01 0 0.02 65(known) (B) a t-.0 O

v P V 0 1 c'1-1 -NH s-cn. c o 0.02 I 100 I 0.004 50 EXAMPLESRhopalosiphum test (systemic action) Solvent: 3 parts by weight ofacetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Toproduce a suitable preparation of active compound, 1 part by weight ofthe active compound was mixed with the stated amount of solventcontaining the stated amount of emulsifier and the concentrate wasdiluted with water to the desired concentration.

Oat plants (Avena sativa), which had been strongly infested with thebird cherry aphid (Rhopalosiphum padi), were watered with thepreparation of the active compound so that the preparation penetratedinto the soil without wetting the leaves of the oat plants. The activecompound was taken up by the oat plants from the soil and thus reachedthe infested leaves.

After the specified periods of-time, the degree of destruction wasdetermined as a percentage: 100% means that all the aphids were killedwhereas means that one of the aphids were killed. L

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 5:

Table 5 EXAMPLE 6 Tetranychus test (resistant) Solvent: 3 parts byweightof acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether Toproduce a suitable preparation of active compound, 1 part by weight ofthe active compound was mixed with the stated amount ofsolventcontaining the stated amount of emulsifier and the concentratewas diluted with water to the desired concentration.

Bean plants (Phasolus vulgaris), which had a height of approximately10-30 cm, were sprayed with the preparation of the active compound untildripping wet. These bean plants were heavily'infested with thetwospotted spider mite Telranychus urticae) in all stages ofdevelopment.

After the specified periods of time, the effectiveness of thepreparation of active compound was determined by counting the deadmites. The degree of destruction thus obtained was expressed as apercentage: means that all the spider mites were'killed whereas 0% meansthat none of the spider mites were killed.

The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 6:

(R/wpulusiplmm test systemic action) Table 6 ('ll'lrunyclzux testresistant) Active compound Active compound Degree of concentrationdestruction in A in V1 after Table 6 -Continucd The process of thisinvention is illustrated in the following preparative Example.

EXAMPLE 7 32.7 (0.20 mole) of chloroacetic acid morpholide in 50 ml ofacetonitrile were added dropwise at room temperature to a solution of62.0 g (0.28 mole) of the sodium salt ofO-ethyl-N-monoisopropy1amido-monothiophosphoric acid in 300 ml ofacetonitrile. The reaction was slightly exothermic. The mixture wasstirred overnight at to C, and the inorganic salts which had separatedout were filtered off. The solvent was removed, the residue was taken upin dichloromethane,

the solution was twice washed with a little water, and

the organic phase was dried over sodium sulfate and filtered. Thefiltrate was concentrated and S- (morpholidocarbonyl)-methyl-O-ethy1-N-monoisopropyl-monothiophosphoric acid ester amide was obtained as ayellow, viscous, water-soluble oil of refractive index n of 1.5153. Theyield was 40.3 g (64.8% of theory). I

The following compounds were obtained by methods analogous to thatdescribed above.

It will be appreciated that the instant specification and examples areset forth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:

1. An S-(amidocarbonyl)-methyl-monothiophosphoric acid ester amide ofthe formula P R" (l) RNH/ \SCH,CN

in which R and R each independently is alkyl of l to 6 carbon atoms,

R" is alkyl or alkenyl of l to 6 carbon atoms optionally carrying atleast one chlorine, C -C alkoxy or C C alkylmercapto radical,

R' is hydrogen or acyl with the proviso that R is not hydrogen is R" isunsubstituted alkyl.

2. A compound according to claim 1, in which R and R each independentlyis alkyl of 1 to 4 carbom atoms; R" is ally] or alkyl of l to 4 carbonatoms optionally carrying at least one chlorine, C C alkoxy or C -Calkylmercapto group; and R is hydrogen or a formyl, acetyl, propionyl,butyryl, isobutyryl or benzoyl radical.

3. The compound according to claim 1, wherein such compound isS-(methoxymethylamidocarbonyl)- 20methyl-O-ethyl-N-monoisopropyl-monothiophosphoric acid ester amide ofthe formula 4. The compound according to claim 1, wherein such compoundis S-(N-acetyl-isopropylamidocarbonyl)-methyl-O-ethyl-N-monoisopropyl-monothiophosphoric acid ester amide ofthe formula P i-C,H,-NH s-curfiqu 5. The compound according to claim 1,wherein such compound is S-(N-isobutyryl-methylamidocarbonyl)-methyl-O-ethyl-N-monoisopropyl-monothiophosphoric acid ester amide ofthe formula

1. AN S-(AMIDOCARBONYL)-METHYL-MONOTHIOPHOSPHORIC ACID ESTER AMIDE OFTHE FORMULA
 2. A compound according to claim 1, in which R and R'' eachindependently is alkyl of 1 to 4 carbom atoms; R'''' is allyl or alkylof 1 to 4 carbon atoms optionally carrying at least one chlorine, C1-C6alkoxy or C1-C6 alkylmercapto group; and R'''''' is hydrogen or aformyl, acetyl, propionyl, butyryl, isobutyryl or benzoyl radical. 3.The compound according to claim 1, wherein such compound isS-(methoxymethylamidocarbonyl)-methyl-O-ethyl-N-monoisopropyl-monothiophosphoric acid ester amide of the formula
 4. The compoundaccording to claim 1, wherein such compound isS-(N-acetyl-isopropylamidocarbonyl)-methyl-O-ethyl-N-monoisopropyl-monothiophosphoric acid ester amide of the formula
 5. The compoundaccording to claim 1, wherein such compound isS-(N-isobutyryl-methylamidocarbonyl)-methyl-O-ethyl-N-monoisopropyl-monothiophosphoric acid ester amide of the formula